Basic dyestuffs

ABSTRACT

The present invention relates to basic dyestuffs with a dibenzofuran system, their mixtures, processes for their manufacture and their use for dyeing and printing of natural and synthetic materials; particularly of polyacrylonitrile and copolymers of acrylonitrile with other vinyl compounds, and acid modified aromatic polyesters and acid modified polyamides, leather, tanned cotton, cellulose, polyurethanes and for the production of writing liquids and stamping inks.

United States Patent 1 Kuhlthau 1 1 BASIC DYESTUFFS \[75] inventor: Hans-Peter Kuhlthau, Leverkusen,

Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen-Bayerwerk, Germany 122] Filed: Mar. 9, 1973 1121] Appl. No.2 339,889

130] Foreign Application Priority Data Mar. 11, 1972 Germany 2211958 \[52] US. Cl. 260/240 G; 8/12; 8/54.2;

13/177 R; 8/178 E; 8/178 R; 8/179; 106/22;

260/37 NP; 260/37 P; 260/326.11

\[51 1 Int. Cl C09b 23/00 158] Field of Search 260/240 G, 240.8, 326.16

[[56] References Cited UNITED STATES PATENTS 3,345,355 10/1967 Raue 260/165 3,673,178 6/1972 Tewksbury et a1. 260/240.8 3.759.902 9/1973 Kuhlthau ct a1. 260/240.8

FOREIGN PATENTS OR APPLICATIONS 1,214,896 11/1959 France 260/240 G [451 July 29,1975

OTHER PUBLICATIONS Chemical Abstracts, Vol. 57, cols. 792 to 793 (1962), (abst. of Schroeder et al.).

Chemical Abstracts, Vol. 51, cols. 12065 to 12066 (1957), (abst. of Langenbeck et a1.).

Chemical Abstracts, Sixth Collective Index, subjects A-Bi, p. 1582 (1964) benzofuroindole".

Primary Examiner.lohn D. Randolph Attorney, Agent, or FirmPlumley & Tyner [57] ABSTRACT 14 Claims, No Drawings BASIC DYESTUFFS The present invention relates to basic dyestuffs of the formula denotes the remaining members of a dibenzofu rane system,

1R, denotes alkyl, aralkyl or cycloalkyl.

R denotes alkyl, aralykyl aralkyl cycloalkyl, it being possible for R and R to join together in a cycloallkyl ring,

R, denotes hydrogen, alkyl, aryl or aralkyl,

3R, denotes a non-ionic substituent.

lR denotes hydrogen or an alkyl radical which can :form, with the o-position of the ring B, a ring which can be condensed with a further carbocyclic ring; cycloalkyl or aralkyl,

Y denotes CH or N,

m denotes the numbers 0, l or 2 and .W" denotes an anion.

Additionally, mixtures of the dyestuffs 1, their manufacture and use for dyeing and printing natural and synthetic materials are a subject of this invention. The ring B can be fused to further rings. The cyclic and acyclic radicals can contain further non-ionic substituents and- ,lor carboxyl groups.

Examples of suitable substituents of the ring system A are: halogen, nitro, alkyl with 14 C atoms, benzyl, phenethyl. hydroxyl, alkoxy with l-4 C atoms, phenyiloxy. lbenzyioxy or acyl with l-3 C atoms in the alkyl radical.

Examples of suitable substituents of the ring B are: halogen, nitrile, nitro. alkyl with 1-4 C atoms, benzyl, phencthyl, cyclohexyl, hydroxyl, alkoxy or alkylthio with l-l 2 C atoms, phenyloxy, phenylthio, benzyloxy, benzylthio. amino, alkylamino with l-4 C atoms, acylamino with l3 C atoms in the alkyl radical, benzoylamino, carboxyl. alkoxycarbonyl with l-4 C atoms in the alkyl radical, aminocarbonyl or aminosulphonyl.

An alkyl radical is understood as a saturated or unsaturated. optionally substituted, aliphatic hydrocarbon radical of, preferably. l6 C atoms, such as methyl, triifluoromethyl, ethyl. chloroethyl, bromoethyl, hydroxyethyl, methoxyethyl, cyanoethyl, acetoxyethyl, aminocarbonylethyl, i-propyl. n-butyl, i-butyl, t-butyl, i-amyl, allyl. methallyl, y-chlorallyl or propargyl.

Examples of possible aralkyl radicals are: phenylmethyl, phenylethyl, phenylpropyl-( 2,2) and optionally their derivatives substituted in the phenyl nucleus.

As cycloalkyl, cyclohexyl is of particular importance.

Aryl represents carbocyclic aromatic structures with b-IIO carbon atoms such as phenyl and naphthyl and their derivatives such as 4-methylphenyl, 2- methylphenyl. 4-chlorophenyl. Z-chlorophenyl and 2-methy'l-l-chloro-phenyl.

Non-ionic substituents in the sense of the presentinvention are the non-dissociating substituents which are customary in dyestuff chemistry. such as fluorine. chlorine and bromine; alkyl groups, especially straightchain or branched alkyl radicals with l-6 C atoms; aralkyl radicals; alkenyl radicals; aryl radicals; alkoxy radicals, especially alkoxy radicals with l4 C atoms; aralkoxy radicals; aryloxy radicals and alkylthio radicals, preferably alkylthio radicals with l-3 C atoms; aralkylthio radicals; arylthio radicals; nitro; nitrile; alkoxycarbonyl, preferably those having an alkoxy radical with l-4 C atoms; the formyl radical; alkylcarbonyl radicals, especially those having an alkyl group with l-4 C atoms; arylcarbonyl; aralkylcarbonyl radicals; alkoxycarbonyloxy radicals, preferably having an alkyl group with l4 C atoms; alkylcarbonylamino radicals. preferably having an alkyl group with l-4 C atoms, and arylcarbonylamino radicals; alkylsulphonylamino radicals, preferably having an alkyl group with l-3 C atoms; arylsulphonylamino groups, ureido; N-arylor N-alkyl-ureido, aryloxycarbonylamino and alkoxycarbonylamino; carbamoyl; N-alkyl-carbamoyl; N,N-dialkylcarbamoyl; N-alkyl-N-arylcarbamoyl; suulphamoyl; N-alkylsulphamoyl; N,N-dialkylsulphamoyl; alkylsulphonyl; alkenylsulphonyl; aralkylsulphonyl. with 14 C atoms preferably being present in the alkyl radicals mentioned; arylsulphonyl and carboxylic acid alkyl ester, carboxylic acid aryl ester, sulphonic acid alkyl ester and sulphonic acid aryl ester groups.

Possible anionic radicals X are the organic and inorganic anions which are customary for cationic dyestuffs.

Examples of inorganic anions are fluoride, chloride, bromide and iodide, perchlorate, hydroxyl, and radicals of acids containing S, such as bisulphate, sulphate, disulphate and aminosulphate; radicals of nitrogenoxygen acids, such as nitrate; radicals of oxygen acids of phosphorus such as dihydrogenphosphate; hydrogen-phosphate, phosphate and metaphosphate; radicals of carbonic acid, such as bicarbonate and carbonate; further anions of oxygen acids and complex acids, such as methosulphate, ethosulphate, hexafluosilicate, cyanate, thiocyanate, ferrocyanide, ferricyanide, trichlorozincate and tetrachlorozincate, tribromozincate and tetrabromozincate, stannate, borate, divanadate, tetravanadate, molybdate, tungstate, chromate, bichromate and tetrafluoborate, as well as anions of esters of boric acid, such as of the glycerine ester of boric acid and of esters of phosphoric acid, such as of methyl phosphate.

Examples of organic anions are anions of saturated or unsaturated aliphatic, cycloaliphatic, aromatic and heterocyclic carboxylic acids and sulphonic acids, such as radicals of acetic acid, chloroacetic acid, cyanoacetic acid, hydroxyacetic acid, aminoacetic acid, methylaminoacetic acid, aminoethyl-sulphonic acid, methylaminoethyl-sulphonic acid, propionic acid, nbutyric acid, i-butyric acid, Z-methyl-butyric acid, 2- ethyI-butyric acid, dichloracetic acid, trichloroacetic acid, trifluoracetic acid, 2-chloropropionic acid, 3- chloropropionic acid, 2-chlorobutyric acid, 2'hydroxy propionic acid, 3-hydroxypropionic acid, 0- ethylglycollic acid, thioglycollic acid, glyceric acid, malic acid, dodecyltetraethyleneglycol-ether-propionic acid, 3-(nonyloxy)-propionic acid, 3-(isotridecyloxy) propionic acid, 3-(isotridecyloxy)-diethyleneglycolether-propionic acid, the ether-propionic acid of the alcohol mixture with 6 to 10 carbon atoms, thioacetic acid. 6-benzoylamino-Z-chlorocaproic acid, nonylphenoltetraethylene-glycol-ether-propionic acid, nonylphenoldiethylene-glycol-ether-propionic acid, dodecyltetraethyleneglycol-ether-propionic acid, phenoxyacetic acid, nonylphenoxyacetic acid, n-valeric acid, i-valeric acid, 2.2,2-trimethylacetic acid, n-caproic acid, 2- ethyl-n-caproic acid, stearic acid, oleic acid, ricinoleic acid, palmitic acid, n-pelargonic acid, lauric acid, a mixture of aliphatic carboxylic acids with 9 to l 1 carbon atoms (Versatic Acid 91 l of SHELL), a mixture of aliphatic carboxylic acids with to 19 carbon atoms (Versatic Acid 1519 of SHELL), coconut fatty acid first runnings, undecanecarboxylic acid, ntridecanecarboxylic acid and a coconut fatty acid mixture; acrylic acid, methacrylic acid, crotonic acid, proparglyic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, the isomer mixture of 2,2,4- and 2,4,4- trimethyladipic acid, sebacic acid, isosebacic acid (isomer mixture), tartaric acid, citric acid, glyoxylic acid, dimethyl-ether-a,0z-dicarboxylic acid, methylene-bisthioglycollic acid, dimethylsulphide-apt-dicarboxylic acid, 2,2-dithio-di-n-propionic acid, fumaric acid, maleic acid, itaconic acid, ethylene-bis-iminoacetic acid, nitrilosulphonic acid, methanesulphonic acid, ethanesulphonic acid, chloromethanesulphonic acid, 2-chloroethanesulphonic acid and Z-hydroxyethanesulphonic acid, and Mersolat, that is to say C Cis-paraffinsulphonic acid obtained by chlorosulphonation of paraffin oil.

Suitable anions of cycloaliphatic carboxylic acids are, for example, the anions of cyclohexanecarboxylic acid and cyclohexene-B-carboxylic acid and anions of araliphatic monocarboxylic acids are, for example, anions of phenylacetic acid, 4-methylphenylacetic acid and mandelic acid,

Suitable anions of aromatic carboxylic acids are, for example, the anions of benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 4- tert.-butylbenzoic acid, Z-bromobenzoic acid, 2- chlorobenzoic acid, 3-chlorobenzoic acid, 4- chlorobenzoic acid, 2,4-dichlorobenzoic acid, 2,5- dichlorobenzoic acid, 2-nitrobenzoic acid, 3- nitrobenzoic acid, 4-nitrobenzoic acid, 2-chloro-4- nitrobenzoic acid, 6-chloro-3-nitro-benzoic acid, 2,4-

dinitrobenzoic acid, 3 ,4-dinitrobenzoic acid, 3 ,5- dinitrobenzoic acid, Z-hydroxybenzoic acid, 3- hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-

carboxylic acid, 2-hydroxy-l-naphthoic acid and anthraquinone-Z-carboxylic acid.

Suitable anions of heterocyclic carboxylic acids are, for example, the anions of pyromucic acid, dehydromucic acid and indolyl-3-acetic acid.

Suitable anions of aromatic sulphonic acids are, for example, the anions of benzenesulphonic acid, benzene-1,3-disulphonic acid, 4-chlorobenzenesulphonic acid, 3-nitrobenzenesulphonic acid, 6-chloro-3 nitrobenzenesulphonic acid, toluene-4-sulphonic acid, toluene-2-sulphonic acid. toluene-w-sulphonic acid, 2-chlorotoluene-4-sulphonic acid, l-hydroxybenzenesulphonic acid, n-dodecylbenzenesulphonic acid, 1.2,- 3,4-tetrahydronaphthalene-o-sulphonic acid, naphthalene-l-sulphonic acid, naphthalene-l,4- or l ,S-disulphonic acid, naphthalenel ,3,5-trisulphonic acid, l-naphthol-Z-sulphonic acid, S-nitronaphthalene- Z-sulphonic acid, S-aminonaphthalene-l-sulphonic acid, stilbene-2,2'-disulphonic acid and biphenyl-Z- sulphonic acid.

A suitable anion of heterocyclic sulphonic acids is, for example, the anion of quinoline-S-sulphonic acid.

Further possibilities are the anions of arylsulphinic, arylphosphonic and arylphosphonous acids, such as benzenesulphinic and benzenephosphonic acid.

Colourless anions are preferred. For dyeing from an aqueous medium, anions which increase the solubility of the dyestuff in water are preferred, for example the formate, acetate or lactate anion or an anion of an aliphatic dicarboxylic acid such as of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, maleic acid or itaconic acid. For dyeing from organic solvents, anions which assist the solubility of the dyestuff in organic solvents or at least do not influence it adversely are frequently also preferred.

The anion is generally determined by the manufac turing process and by the purification of the crude dye stuff which may have been carried out. In general, the dyestuffs are present as halides (especially as chlorides or bromides) or as methosulphates, ethosulphates, sulphates, benzenesulphonates or toluenesulphonates, or as acetates. A replacement of dyestuff anions by other dyestuff anions can be carried out by treating the basic dyestuff with acid-binding agents such as sodium carbonate, potassium carbonate, ammonium carbonate, magnesium carbonate, sodium hydroxide, potassium hydroxide, ammonia and silver oxide, optionally in an aqueous medium, whereupon the dyestuff-onium base (or the carbinol base) is produced, and treating the base with anion-donating agents.

Dyestuffs of the following general formulae, and their mixtures, are of interest:

II a

1 R (a 2 P (11.

(R whoa-1i K3 7)m X wherein R R R;;, X and m have the abovementioned meaning and wherein 1E denotes an alkylene radical with 2 or 3 C atoms.

1R denotes halogen, nitro, alkyl, aralkyl, hydroxy,

alkoxy. aryloxy, aralkyloxy or acyl,

R denotes halogen, nitrile, alkyl, aralkyl, hydroxy, ulkoxy. aryloxy, aralkyloxy, alkylthio, arylthio, aralkylthio, amino, acylamino, carboxy or alkoxycarbonyl and n denotes the numbers 0, l and 2.

Mixtures of llb and llc are preferred, and mixtures of lla and lld are particularly preferred. At the same time, mixtures of the compounds [la and lld in which n O are of particular importance. The last-mentioned mixtures are particularly preferred if R, and R are methyl groups and R represents n-propyl, i-propyl, n-butyl, ,B-chloroethyl. B-hydroxyethyl, B-cyanoethyl, B-methoxyethyl. ,B-bromoethyl. allyl, B-acetoxyethyl or benzyl, but very particularly preferentially represents methyl or ethyl.

Dyestuffs and their mixtures of the following general formulae are also valuable:

III a,

6 n o N on wit 3 III mea

wherein R,, R R R R X, m and n have the abovementioned meaning and wherein R,, denotes hydrogen, alkyl with l-4 C atoms, benzyl or phenylethyl.

Mixtures of lllb and lllc are preferred and mixtures of Illa and llld are particularly preferred. At the same time, mixtures of the "compounds llla and llld in which n Q are of particular importance. The last-mentioned mixtures are particularly preferred if R, and R are methyl and R represents n-propyl, i-propyl. n-butyl. B-chloroetliyl'; B-hydroxyethyl, B-cyanoethyl. B-methoxyethyl, ,B-bromoethyl, allyl, ,B-acetoxyethyl or benzyl, but very particularly preferentially represents methyl or ethyl, and if R,, represents methyl or ethyl.

The dyestuffs of the formula I and their mixtures are manufactured, in the case that Y CH, by condensation of aldehydes or their functional derivatives of the formula n n Hit 2 IV N CH C1D l s with amines of the formula n it v 1; l v RI in a manner which is in itself known.

In the formulae IV and V, R R R R R A and m have the meaning indicated for the formula I.

Examples of suitable functional aldehyde derivatives are azomethines and their salts, hydrazones, oximes, acetals, hydrates, ammoniates, aminals or bisulphite adducts.

The condensation can be carried out by stirring the solution or suspension of equimolar amounts of the compound W and V in an organic or inorganic acid or their mixtures with water at lOl2()C, preferably at 2060C. Dilute aqueous mineral acids such as .sulphuric acid, phosphoric acid or hydrochloric acid, for example, are suitable. Lower fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid and their mixtures with water are also suitable.

The condensation can also be carried out in an inert solvent such as, say, acetonitrile, methanol, ethanol,

isopropanol, toluene or chlorobenzene in the presence of acid condensation agents such as, say, phosphorus oxychloride, phosphorus pentoxide, zinc chloride, aluminum chloride, tin chloride, sulphuric acid, phosphoric acid or polyphosphoric acid.

A particular embodiment of the process according to the invention is characterised in that aldehydes of the formula IV, in the form of their enamines as first produced in the Vilsmeier reaction, of the formula u on cu N c1 I R R3 10 wherein R,, R R and A have the meaning indicated for formula l and R represents C -C alkyl or phenyl and R represents C -C alkyl are employed.

Examples of suitable aldehydes of the formula IV are:

7 Mixtures of the substances:

8. Mixtures of the substances:

l. Mixtures of the substances: l5 CH and l: I a ,cn cu r cu cm mm 0 cn-cno 30 0c 2. Mixtures of the substances: on

CH-CHO Br CH I 3 CH 0 u -cno and cfl'cm 1 11 3. Mixtures of the substances:

m w 0 N cu CHO l ca CH 3 3 0 As examples of amine components of the formula V n cm there may be mentioned: 4-aminodiphenyl-ether, 4- u e on ammo-4'-methyl-diphenyl-ether, 4-ammo-4- 4. 3 ethyldrphenyl-ether, 4-ammo-4'-tertrarybutyldiphenyl-ether, 4-amino-4-cyclohexyldiphenyl- N0 ether, 4-amino-2'-methyldiphenyl-ether, 4-amino-3- methyldiphenyl-ether, 4-amino-4'-methoxy-diphenyl- 0 ether, 4-amino-3'-methoxy-diphenyl-ether, 4-amino- CH cm 4'-ethoxy-diphenylether, 4-amino-4-4'-acetylamino- "c diphenyl-ether, 4-amino-4'-hydroxy-diphenyl-ether, 3 CH3 4-amino-4-nitrodiphenyl-ether, 4-amino-4- chlorodiphenyl-ether, 4-amino-2-chlorodiphenyl- 5. Mixtures of the substances: ether, 4-amino-3-chlorodiphenyl-ether, 4-aminophenyl-a-naphthylether, 4-aminophenyl-B-naphthylc and ether, 4-amino-2 ',3 ',5 '-trimethyldiphenyl-ether, c 4-aminophenylbenzyl-ether, 3-aminophenylbenzyl- 3 ether, 2-amino-phenylbenzyl-ether, 2-aminodiphenyl- 0 N CH cm ether, 4-amin0phenyl-p-methylbenzyl-ether, 4-

l e 0 N,CH3 ammophenyl-p-chlorobenzyl-ether, 4-amm0phenyl-o chlorobenzyl-ether, 4-ammophenyl-m,p- 6O dichlorobenzylether, 4-amin0benzyl-2,4',5-tri- "3 chlorobenzyl-ether, B-aminophenyl-p-methylbenzyl- 6, ether, 3-aminophenyl-p-chlorobenzyl-ether, 3 H C CH aminophenyl-o-chlorobenzyl-ether, 3-aminophenyl- 3 CH m,p-dichlorobenzyl-ether, 3-aminophenyl-2,4,5'-trio 3 chlorobenzyl-ether, 2-aminophenyl-p-methylbenzyl- CH'CHO ether, Z-aminophenyl-p-chlorobenzyl-ether, 2- aminophenyl-m,p-dichlorobenzyl-ether, 2-

aminophenyl-2,4,5'-trichlorobenzyl-ether, 4-amino- 9 I3-methylphenyl-benzyl-ether, S-amino-Z-methyLphenyl-benZyl-ether, 2-amino-S-methyl-phenyl-benzylether. 4-amino-2-methoxy-phenylbenzylether. 4 amino-3-methoxy-phenyl-benzyl-ether, 4-amino-3- methyl-phenyl-benzyl-ether, 4-amino-3-chloro-phenylbenzylether, 4-amino-2-chloro-phenyl-benzyl-ether. d-amino-2'methylphenyl-pmethylbenzyl-ether, 5- amino-lmethyl-phenyl-m,p-dichlorobenzyl-ether, 2- amino-S-methyl-phenyl-p-chlorobenzylether. 4-amino- 3-methoxy-phenyl-p-methylbenzyl-ether, 4 -amino-3- methyl-phenyl-2,4'.5'-trichlorobenzyl-ether, aniline. p-toluidine, m-toluidine, o-anisidine, m-anisidine. punisidine. p-phenetidine, o-phenetidine. 4- tiodecyloxyaniline, 4-aminoacetanilide. N-benzoyl-pphenylenediamine. 2,4dimethoxyaniline, 7 5- dimethoxyaniline, 3,4-dimethoxyaniline, 2-chloro-4- 2,4.5-trimethylaniline, 2.3 .5-

S-amino-Z-acetylaminoanisole.

3.4-dicyanoaniline, p-

VI I

wherein R R and m have the meaning indicated for formula with methyleneindolines of the formula 2 a VIII a wherein R R R and A have the meaning indicated for the formula (I) under acid conditions.

For example, the procedure followed is to heat a component of the formula (V) and formic acid to the boil in an inert water-immiscible solvent, such as benztene. toluene or chlorobenzene until the water formed has been separated off azeotropically, mix the resulting solution of a compound of the formula (VII) with the equivalent amount of an indolinemethylene compound of the formula (Vlll), add an acid condensation agent such as phosphorus oxychloride, phosphorus pentoxide, polyphosphoric acid or sulphuric acid and carry out the condensation in the temperature range of 20 to 100C.

Dyestuffs of the formula 1 and their mixtures in which Y N and R3 is not cyclised are manufactured by protonising or quaternising azo bases or their mixtures, of the formula wherein R R R R, n and A have the same meaning as in the formula I with compounds R' -X wherein R,-, denotes hydrogen, alkyl, cycloalkyl or aralkyl and X is a radical which can be split off as an anion. Azo bases of the formula IX can be manufactured by diazotising, in a manner which is in itself known, amines of the formula wherein R and m have the meaning mentioned for formula I and coupling with Compounds of the formula VI, and treating the resulting coupling products with alkali in a manner which is in itself known.

The coupling products of the formula IX and their mixtures have the following formula in an acid medium x IX a The alkylation can be carried out by warming the sollution or suspension of a compound of the formula [X in an inert medium with the alkylating agent to 60-150C, preferably -l20C. For this purpose, an excess of the alkylating agent can also be used as the solvent.

Suitable inert media are, for example, organic liquids such as benzine, ligroin, cyclohexane, benzene, toluene, chloroform. chlorobenzene and dichlorobenzene, nitrobenzene, tetralin, dioxane, acetonitrile and dimethylformamide.

Suitable alkylating agents are, for example, dimethyl sulphate, diethyl sulphate, di-n-butyl sulphate, di-isoamyl sulphate, dimethyl pyrosulphate, benzenesulphonic acid methyl, ethyl, n-propyl, iso-propyl and isobutyl ester, toluenesulphonic acid methyl, ethyl, npropyl, iso-propyl and isobutyl ester, mthyl iodide. ethyl iodide, n-butyl bromide, allyl bromide, 2-chloroand Z-bromo-diethyLether as well as chloroacetic and bromoacetic acid esters such as chloroacetic and bromoacetic acid ethyl esters.

The alkylation can also be carried out in the presence of alkaline agents especially in the presence of tertiary amines, which have a bulky substituent at the N-atom. in accordance with Belgian Patent Specification No. 735.565. Triisopropanolamine is particularly suitable as an amine with bulky substitution.

Suitable amine compounds of the formula Va are amines of the formula V in which R denotes a hydrogen atom.

Suitable methylene compounds of the formula Vlll have already been listed above in the form of their w-aldehydes of the general formula IV.

Dyestuffs of the formula I and their mixtures, in which Y N can also be obtained by reaction of compounds, or their mixtures, of the formula 1 ll l z X N cu=Z I a wherein A, R R and R have the same meaning as in the formula I and Z denotes oxygen or a a functional derivative of the aldehyde group with compounds of the formula 4 fl N-Ng m wherein R R and m have the same meaning as in the formula l.

The new dyestuffs and their mixtures of the formula I are valuable dyestuffs which can be used for dyeing and printing materials of leather, tannin-treated cotton, cellulose, synthetic polyamides and polyurethanes, and for dyeing fibres containing lignin, such as coir, jute and sisal. They are furthermore suitable for the manufacture of writing fluids, rubber-stamp inks and ball pen pastes and can also be used in flexographic printing.

Flocks, fibres, filaments, tapes, woven fabrics or knitted fabrics of polyacrylonitrile or of copolymers of acrylonitrile with other vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl ace tate, vinylpyridine, vinylimidazole vinyl alcohol, acrylic and methacrylic acid esters and amides and asymmetrical dicyanoethylene, or flocks, fibres, filaments, tapes, woven fabrics or knitted fabrics of acid-modified aromatic polyesters and acid-modified polyamide fibres are particularly suitable for dyeing with the basic dyestuffs, and their mixtures, of the formula 1. Acidmodified aromatic polyesters are, for example, polycondensation products of sulphoterephathalic acid and ethylene glycol, that is to say polyethyleneglycoltereph thalates containing sulphonic acid groups (type Dacron 64 of E. l. DuPont de Nemours and Company) such as are described in Belgian patent specification. No. 549,179 and US. Pat. No. 2,893,816.

Dyeing can also be effected from a weakly acid liquor. with the material appropriately being introduced into the dyebath at 40-60C and then dyed at the boil. It is also possible to dye under pressure at temperatures above l00C. Furthermore, the dyestuffs can be added to spinning solutions for the manufacture of fibres containing polyacrylonitrile or be applied to the unstretched fibre. The greenish-tinged yellow to orangecoloured dyeings on polyacrylonitrile, acid-modified polyesters and acid-modified polyamide are distinguished by very good fastness to light, wet processing, rubbing and sublimation and by a high affinity to the fibre. The fibres form light-fast pigments which anionic precipitants such as alumina, tannin, phosphotungstic acids and phosphomolybdic acids, and these pigments can advantageously be employed in paper printing.

The dyestuffs can be used individually or as mixtures.

The dyestuffs according to the invention and their mixtures are very suitable for dyeing shaped articles of polymers or copolymers of acrylonitrile, asymmetrical dicyanoethylene. acid-modified aromatic polyesters or acidmodified synthetic polyamides in chlorinated hydrocarbons as the dyebath, if they carry substituents which assist the solubility in chlorinated hydrocarbons. such as, for example, the tertiary butyl group or the dodecyloxy group, or if the anion Xis the anion of a monobasic organic acid with 4-30 carbon atoms.

Stable concentrated solutions of these dyestuffs in chlorinated hydrocarbons can in particular then be manufactured, optionally with addition of polar or ganic solvents which are completely miscible with chlorinated hydrocarbons, such as butyrolactone, dimethylformamide, methanol, dioxane, acetonitrle, methyl ethyl ketone, nitrobenzene, dimethylsulphoxide, benzonitrile and Z-nitrochlorobenzene, if the dyestuffs according to the invention are in the form of salts of the monobasic organic acids with 4-30 carbon atoms which have been mentioned.

To manufacture such solutions, the dyestuffs according to the invention, or their mixtures (in the form of the free bases or as salts of organic acids with 430 carbon atoms) are stirred with chlorinated hydrocarbons and monobasic organic acids with 430 carbon atoms, optionally with the addition of polar organic solvents which are completely miscible with chlorinated hydrocarbons, and optionally at an elevated temperature.

EXAMPLE 1 7 29,] parts by weight of an aldehyde mixture Xll which consists of the components as obtained according to Example 227, and 13.3 parts by weight of 2-methyl-2,B-dihydroindole are stirred with 60 parts by volume of glacial acetic acid and 15 parts by volume of water for 4 hours at room temperature and then diluted with 1,000 parts by volume of water. The resulting dyestuff mixture is salted-out with 50 parts by weight of sodium chloride, separated from the solution, re-dissolved in 1,500 parts by volume of water, again salted-out with sodium chloride, separated off and dried.

, It consists to the extent of about 44 percent of the component of the formula und to the extent of about 56 percent of the component of the formula and dyes materials of polyacrylonitrile, acid-modified polyesters and acid-modified polyamide in greenishtinged yellow shades of excellent fastness to light and to wet processing.

EXAMPLE 2 if in Example 1, an aldehyde mixture Xlll of the components Mixture XIII and cu-cno Example No. Aldehyde Mixture No.

Xll Xlll Xll Xlll Xll Xlll Xll Xlll Xll Xlll Xll wu-ccaeazrmzw 2,3.3-Trimethyl-S-methoxyindolinc 2 3.3-Trimethyl5ethoxyindolinc 2.3.3-Trimcthyl-5herixyloxyindoline 2,3.3-Trimethyl-5phenoxyindoline is employed, which is obtained according to Example 227 if instead of Laminobenzofurzme 2- uminobenzofurane is reacted, and in other respects the instructions in Example 1 are followed, a mixture is obtained which consists to the extent of about 73 percent of the dyestuff and to the extent of about 27 percent of the dyestuff o c11 c" I I v H on N C1 3 v CH It has similarly good dyeing properties to the dyestuff mixture described in Example 1.

Analogously, the following valuable dyestuff mixtures are obtained on using other amines than 2- methylindoline for the condensation with the abovementioned aldehyde mixtures XII and Xlll:

Colour Shade on Polyacrylonitrile Amine greenish-tinged yellow curbazolc Xlll Xll Xlll Xll 1.2.3 .4-Tctrzthydro-o-mcthoxyquinolinc S-Methoxyindolinc S-Ethoxyindoline L23 .4-Tctrahytlroquinoxulinc 6.7-Dimethyl2.3-dihydro-4-H-henzoxazine I .4)

2.2,4-TrimcthyL I ,2.3.4-tctrahydroquinolinc 3,4-Tctrahydro-o-ethoxyquinoline ontmucd l \Jl'HPlL Mr '\l4lLl'l\\lC \lntuu- \i Ammo Colour Shade on Polyacrylonitrilc ll IU 4-(yclohcxylunilinc yellow l l l l-l-Diethoxyuniline reddish-tinged yellow ll :2 Z-Aminonuphthulenc yellow l l3 p-tcrtv-Butyluniline greenish-tinged yellow ll l4 p-n-Propoxyunilinc ll l5 p-n-Butoxyuniline ll {fr p-i-Propoxyunilinc l I? Xlll p Toluidine l IX p-lert.-But vluniline l I) p-Anisidine On using the appropriate startingg products and employing the procedure indicated in Example 1, the following dyestuffs are obtained:

R R 12 \SO 0 2 Structure XIV x o 1: cu on R Structure XV x- 13 H. CH 14 I 1 12 R2 Structure XVI it on ca N 13 I R Structure XVII Example Structure R R: R R,; R R, R R Colour Shade on No. Polyacrylonitrile ll 10 Mixture of XI\' CH CH OH; H H H H greenish-tinged yellow und XV CH3 CH3 (1H5 H H H H H l: ll lMixture Of XIV CH3 CH3 CQH}, H OCHZ: CH3 CH3 l,

und (V CH3 CH3 (:H H H OCHJI CH3 CH" l 3'. Mixture of XlV CH CH CH Br H H H untl XV CH; CH CH; Br H H H H ll 23 Mixture of XVI CH CH H H H H 1,

Wind XVll CH CH (1H,, H H I H \24 Mixture of xvi CH (H H, C (2H3 a llnd XVII cu CH O L U 3 C ontmued Example Structure R R R R R R R R, Colour Shade on No. Polyacrylonitrile I XV CH CH CH CH CH; H H H 12o XV CH;, CH, CH H OCH H H H I27 XV CH: CH CH H COCH H H H IZK Mixture of XIV CH CH CH CH, H H H and XV CH CH CH CH H H H I29 Mixture ol XIV C H; C. -H,-, (:H; H H H H and XV H, H; H H H H H H 130 Mixture of XIV CH CH; Benzyl H H H H H and XV I3l Mixture of XIV CH CH, CH-= H H H H CH(H and XV I32 Mixture of XIV CH CH I CH- CH- H H H H H ,-CN and XV I33 Mixture of XIV CH,, CH, CH -CH H H H H H ,-Cl and XV I 34 XV CH CH CH H Br H H H yellow I35 Mixture of XIV CH CH n-C. H,. H H H H H greenish-tinged yellow and XV EXAMPLE I36 chlorobenzene is dehydrated by distilling off about Mixture XVIII are dissolved in 50 parts by volume of acetonitrile.

The mixture of the indolines was manufactured ac cording to Example 227.

At the same time, 10.5 parts by weight of p-anisidine in 300 parts by volume of water are diazotised with a solution of 5.9 g of sodium nitrite in 25 parts by volume of water in the presence of 30.9 parts by weight of 30 percent strength hydrochloric acid. The excess nitrite is destroyed with amidosulphonic acid, 0.5 parts by weight of an emulsifier is added and the above solution is allowed to run into acetonitrile at 5. 75 parts by volume of a 20 percent strength sodium acetate solution are then added dropwise over the course of 3 hours and at the same time the temperature is raised to 10C. Finally. the temperature is allowed to rise to l820C and the coupling product is then salted-out. It is filtered off in the form of a red powder and is then introduced at 80C into a stirred mixture of 200 parts by volume of chlorobenzene and 200 parts by volumeof water. whilst at the same time keeping the pH-value of the aqueous layer at 9-10 by dropwise addition of sodium hydroxide solution. The mixture is stirred for a further 30 minutes. the organic layer is separated off. 3.3 parts by weight of triisopropanolamine are added and the ml ofliquid under reduced pressure at approx. C. l4 parts by weight of dimethylsulphate are then added dropwise at 80C and stirring is continued until the methylation is complete, which can be followed by thin layer chromatography. On cooling. the dyestuff mixture crystallises out.

Its components correspond to the formulae CH CH o t CH=N-N 00011 cii and

S04CH3 The mixture can be isolated by filtering with chlorobenzene solution or, after steam-stripping the chlorobenzene, by filtration of the aqueous distillation residue.

The mixture dyes materials of polyacrylonitrile in orange-coloured shades of excellent fastness to light and to wet processing.

Instead of dimethyl sulphate it is possible to use, for example. diethyl sulphate or ptoluenesulphonie acid methyl ester with equally good result.

EXAMPLE I37 Similar dyeings with similarly good properties on polyacrylonitrile are obtained with the dyestuff mixture of which the components have the structures CH 3 CH I W I 50 CH err N N ocn 4 3 N on and l 3 2 CH 5 CH and It is obtained analogously to the instructions in Example I36 if instead of the indoline mixture there the Mixture XIX is employed. of which the components have the formulae Mixture XIX It is obtainable according to Example 227 if instead of 3-aminobenzofurane Z-aminobenzofurane is employed.

Analogously. the following valuable dyestuff mix- IS tures are obtained when using other amines than panisidine for coupling to the indoline mixtures XVIII or XIX.

The colour shades indicated describe the colouration on polyacrylonitrile. The dyestuffs were redissolved in water and precipitated with sodium chloride. They are thus in the form of the chloride.

Example lndoline Amine Colour Shade on Poly- No. Mixture No. acrylonitrile I38 XVIII 3-AminophcnyIhenzyI-ether golden yellow I39 Z-AminophcnyIbenzyl-ether reddish-tinged yellow I40 4-Aminophenylbenzyl-ether yellowish-tinged orange I 4 I 4-AminophenyI-p'methyl-henzyI-ether I42 4-AminophenyI-p-chIoro-benzyI-ether I43 4-AminophenyI-o chIoro-henzyI-ether I 44 4-Aminophen yl'm p-dichloro-benzyl-ethcr I45 3-AminophenyI-p-methyI-benzyl-ether golden yellow I 46 Z-Aminophen yI-p-methyl-benzyI-ether I47 Z-Aminophen yl-p-chloro-benzyl-ether I48 Z-Aminophen yI-m .p-dichIoro-benzyI-ether I49 4-AminoZ-methyl-phenyl-benzyl-ether yellowish-tinged orange I 50 5-Amino-2-methyI-phenyI'henzyI-ether I5I 2-Amino-5-methyIphenyl-benzyl-ether golden yellow I52 4-Amin6-3-methoxy-phenyl-benzyl-ether yellowish-tinged orange I53 4-Amino-2-methoxy-phenyl-benzyl-ether orange I54 4-Amino-3-methyl-phenyl-henzyI-ether yellowish-tinged orange I 55 4-Amino-3-chloro-phenyl-benzyI-ether I56 4-Amino-2-chloro-phenyl-benzyl-ether I57 4-Amino-2-methyI-phenyI-p-methyI-benzyLether I 58 5-Amino-2methyl-phenyI-m,p-dichloro-benzyl-ether I59 2-Amino-5-methyl-phenyl-p-chIoro-benzyI-ether golden yellow I 60 4-Amino-2-methoxy-phenyl-p-methyl-benzyl-ether orange I6I 4-AminodiphenyI-ether yellowish-tinged orange I62 Z-Aminodiphenyl-ether reddish-tinged yellow I63 4-Amino-4'-methyl-diphenyl-ether yellowish-tinged orange I 64 4-Amino-4 -ethyI-diphenyl-ether I65 4-Amino4 -tcrt.-butyl-diphenyI-ether I66 4-Amino-4'-cyclohexyl-diphenyI-ether I67 4-Amino-2-methyI-diphenyl-ether I68 4-Amino-3 '-methyl-diphenyl ether I 69 4-Amino-4 '-methoxy-diphenyl-ether I 70 4-Amino-3 -methoxy-diphenyl-ether l 7 I 4-Amino-4"ethoxy-diphenyI-ether I 72 4-Amino-4-acetylamino-diphenybethcr orange I 73 4-Amino-4'-nitro-diphenyI-ether I74 4-Amino-4-chIoro dIphenyl-ether yellowish-tinged orange I 75 4-Amino-2 '-chIoro-diphenyl-ether I76 4-Amino-3 '-chloro-diphenyl-ether I 77 4-AminophenyI-a-naphthyI-ether I78 4-Aminophen yI-B-naphthyI-ether I 79 4-Amino-2'.3 ,5'-trimethyI-diphenyl-ether I80 4-Aminodiphenylmethane I81 Aniline golden yellow I82 p-Toluidine I 83 m-Toluidine I84 o-Anisidine I 85 o-Phenetidine I86 p-Phcnetidine yellowish-tinged orange I87 4-Aminoacetanilide orange I88 N-BenzoyI-p-phenylenediamine I89 2.4-Dimethoxyaniline yellowish-tinged orange I90 2.5 DimethoxyaniIine I9I 3.4-Dimethoxyanilinc reddish-tinged orange I92 2-(hloro-4-aminoanisole orange 193 2.4.5-Trimethylanilinc yellowish-tinged orange I94 2.3.5-Trimeth \'lanilinc I95 5-Amino-2-acetylaminoanisolc reddish-tinged orange I96 6-Amino-B-methoxyloluene yellowish-tinged orange I97 3.4-Dicyanoaniline orange ('onlinucd Example Indoline Amine Colour Shade on Poly- No Mixture No. acrylonitrilc I98 p-Sulphanilic acid amide yellowish-tinged orange 19*) 4-Aminobcnzamidc 200 4-(hloroaniline 201 4-F1uoroaniline 202 l.23.4 l'ctrahydro-5-aminonaphthalenc 203 4-Amino-2.S-diethoxyhenzoic acid anilidc scarlet 204 4 Aniino-Z-mcthyl-S-methoxybunxanilidc orange 205 4-Cyclohcxylaniline yellowish-tinged orange 206 2.4-Diethoxyaniline 207 2-Aminonaphthalcnc 20S 3.4-[)iisopropoxyaniline scarlet 200 XIX pAnisidine orange 210 o-Anisidine golden yellow 21 1 p-Toluidine 212 3.4-Dimethoxyanilinc reddrsh-tmged orange 213 3.4-Diisopropoxyanilinc reddish-tinged orange 21-1 Aniline golden yellow 21$ p-tert.-Butylanilinc 21o XVIII 217 p-n-Butoxyaniline orange 21h p-n-Propoxyaniline EXAMPLE 219 93.5 g of the dyestuff mixture described in Example 136 are dissolved in 1.500 ml of water at 98-100C and this solution is added dropwise over the course of 6 hours to a solution, kept at C by addition of ice. of 108 g of anhydrous sodium carbonate in 680 ml of water. Thereafter the mixture is stirred for a further hour at 0C. the product is filtered off and washed with water until chloride-free, and the yellowish, powdery product thus obtained (onium base or carbinol base) is stirred in a mixture of 200 ml of water and 19 g of lactic acid (85 percent strength) at room temperature until it has dissolved practically completely. Any small amounts of insoluble matter which may have remained are filtered off and the filtrate is evaporated at 30C and 20 mm Hg. Residue: 83 g of orange-coloured dyestuff mixture, the components of which have the formulae The mixture dyes polyacrylonitrile fabrics in an orange-coloured shade of excellent fastness to light.

EXAMPLE 220 13.8 parts by weight of o-nitroaniline are diazotised in a known manner. Coupling with 26.3 parts by weight of the methyleneindoline mixture No. XVIII mentioned in Example 136 gives a mixture of the dyestuffs c1 and The mixture dyes polyacrylonitrile in yellow shades having good fastness properties.

EXAMPLE 221 25.8 g of 4-nitroso-3-ethoxy-diethy1aniline hydrochloride, 26.3 g of the mixture N0. XVIII of indolinemethylene bases, mentioned in Example 136, ml of methanol, 13.6 g of zinc chloride (anhydrous) and 2.5 g of acetic anhydride are stirred for approx. 1 hour at room temperature. The mixture is introduced dropwise into 1,000 ml of 10 percent strength sodium chloride solution whilst stirring. The blue azomethine is filtered off and dried in vacuo. 32.8 g of this azomethine dyestuff are stirred with 12.8 g of N-amino-Z- methylindoline sulphate in 40 m1 of dimethylformamide for 2 hours at The batch is poured into a mixture of 200 ml of 10 percent strength hydrochloric acid and 200 m1 of 10 percent strength sodium chloride solution. The dyestuff is filtered off and recrystallised from water. It dyes polyacrylonitrile in orangecoloured shades and consists of the components of the formulae and EXAMPLE 222 A polyacrylonitrile fabric is printed with a printing paste which was manufactured in the following manlflf1 30 parts by weight of the dyestuff mixture described in Example 1. 50 parts by weight of thiodiethyliene glycol. 30 parts by weight of cyclohexanol and 30 parts by weight of 30 percent strength acetic acid are covered with 330 parts by weight of hot water and the resulting solution is added to 500 parts by weight of crystal gum (gum arabic as the thickener). Finally, 30 parts by weight of zinc nitrate solution are also added. The print obtained is dried. steamed for 30 minutes and subsequently rinsed. A yellow print of very good fastness properties is obtained.

EXAMPLE 223 Acid-modified polyglycol terephthalate fibres are introduced at 20C. using a liquor ratio of 1:40, into an aqueous bath which per litre contains 3 to 10 g of sodium sulphate. 0.1 to l g of oleyl polyglycol ether (50 mols of ethylene oxide). -l5 g of dimethyl-benzyldodecyl-ammonium chloride and 0.15 g of the dyestuff mixture of which the formula is described in Example l. and which has been adjusted to pH 45 with acetic acid. The bath is heated to 100C over the course of 30 minutes and is kept at this temperature for 60 minutes. Thereafter the fibres are rinsed and dried. A yellow dyeing of very good fastness properties is obtained.

EXAMPLE 224 lPolyacrylonitrile fibers are introduced at 40C. using a liquor ratio of l:40, into an aqueous bath which per litre contains 0.75 g of 30 percent strength acetic acid. 0.38 g of sodium acetate and 0.15 g of the dyestuff mixture described in Example 1. The bath is heated to the boil over the course of 20-30 minutes and is kept at this temperature for 3060 minutes. After rinsing and drying. a yellow dyeing having very good fastness properties is obtained.

EXAMPLE 225 A stock solution is manufactured from 15 parts by weight of the dyestuff mixture mentioned in Example l. l5 parts by weight of polyacrylonitrile and 70 parts lby weight of dimethylformamide and is added to a customary spinning solution of polyacrylonitrile, which is spun in the usual manner. A greenish-tinged yellow dyeing of the very good fastness properties is obtained.

EXAMPLE 2% Acid-motlified synthetic polyamide fibres are introduced at 40, using a liquor ratio of 1:40. into an aqueous bath which per litre contains g of sodium acetate. l to 5 g of oleyl polyglycol ether (50 mols of ethylone oxide) and 0.3 g of the dyestuff mixture described in Example 1 and has been adjusted to pH 4-5 with acetic acid. The bath is heated to 98 over the course of 30 minutes and is kept at this temperature for 60 minutes. Thereafter the fibres were rinsed and dried. A greenish-tinged yellow dyeing of very good fastness properties is obtained.

EXAMPLE 227 The aldehyde mixture XII of the components CH-CHO 0 --Cl'i CH-CHO B C on} is manufactured as follows: 183 g of 3- aminodibenzofurane are diazotised and then reduced to the corresponding hydrazine in the customary manner. If the latter is reacted in a known manner (G. Plancher, B 31, page 1496) with 95 g of methyl isopropyl ketone to give the trimethylindolenine, 190 g of a yellow oil are obtained; this is not purified further but is instead immediately taken up in 300 ml of chlorobenzene. the solution is stirred at room temperature under nitrogen with 562 ml of 50 percent strength sodium hydroxide solution and 200 g of dimethyl sulphate are then added dropwise at 25 over the course of 4 hours whilst stirring vigorously.

The mixture is stirred for a further 2 hours, 1.500 ml of water are added, the whole is heated to and the organic phase is separated off and washed with water. The trimethyl-Z-methylene-indoline mixture thus obtained is then freed of the chlorobenzene in a waterpump vacuum.

Yield: 193 g of a yellow oil which crystallises slowly. 129 g of this mixture. of which the components have the formulae are slowly added at 40 to a mixture of 94.6 g ofphosphorus oxychloride and 49 g of dimethylformamidc. The resulting suspension is mixed for 8 hours at 45 and is then stirred into a mixture of 34.3 g of 45 percent strength sodium hydroxide solution and 1 kg of ice.

The whole is stirred for a further 4 hours and the resulting crystalline aldehyde mixture is filtered off. Yield: 125.6 g.

I claim:

1. Dyestuff of the formula or mixtures ofdyestuffs of the formula wherein A is a dibenzofuranyl radical;

R, and R are C -c -alkyl fluoro-c -c -alkyl, chloro- C -C -alkyl, bromo-c -C -alkyl, hydroxy-c C alkyl, methoxy-c -C alkyl, cyano-c -C -alkyl, acetoxy-C -C -alkyl. or aminocarbonyl-C -C alkyl. C -C -alkenyl, chloro-C -C -alkenyl. phenylmethyl-C -C -alkenyl, phenylethyl-Ci -C alkenyl, phenylpropyl-(2,2)-C -C -alkenyl,

cyclohexyl-C- -C -alkenyl; or, when R and R are joined together, cyclohexyl;

28 chlorobenzyloxy, naphthyloxy. N- phenylcarbamoyl, or phenyloxy substituted by C,- C -alkyl. cyclohe'xyl methoxy. ethoxy.

wherein R R R R m, and X are defined as in claim 1',

R is halo, nitro, C -C -alkyl, benzyl, hydroxy,

phenylethyl, C,-C -alk0xy, phenyloxy, or benzyloxy; and

n is the number 0, l or 2.

3. Dyestuff or mixtures of dyestuffs of claim 1 of the formula 6 n m X- fl CH=CH-N 3 wherein E. R,, R R R R X. m and n are defined as in claim 2.

R is hydrogen, C -C -alkyl fluoro-c -C -alkyl, chloroC -C --alkyl, bromo-C C -alkyl, hydroxy-C C alkyl, methoxy-c -C -alkyl, cyano-C -C -alkyl acetoxy-c -C -alkyl. or aminocarbonyl-C C alkyl. C -C -alkenyl. chloro-C -C -alkenyl. phenyl- C -C -alkenyl, chlorophenyl-C -C -alkenyl, methylphenyl-C -c -alkenyl, naphthyl, phenyl methyl, phenylethyl. or phenylpropyl-(2,2);

R. is halo, cyano. nitro, C,-C -alkyl, benzyl, phenylethyl. cyclohexyl. hydroxy, C,-C, -alkoxy, C,-C,

alkylthio. phenyloxy, phenylthio. benzyloxy. benzythio. amino, C -C -aIkyIamino. benzoylamino. carboxyl. (C,-C -alkoxy) carbonyl.

aminocarbonyl. aminosulphonyl, mcthylbcnzyloxy.

4. Dyestuff or mixtures of dyestuffs of claim 1 of the formula wherein wherein lE R R R;,. R, R.; X m and n are defined us in R R R R R 3 X. m and n are defined as in claim 2. claim 6. 5. Dyestuff or mixtures of dyestuffs of claim l of the 8. Dyestuff or mixtures of dyestuffs of claim 1 f the formula formula wherein wherein lE. 11 2 3 lh X, are defined as m R R R R R R X. m and n are defined as in claim 2. claim 6. Dyestuff or mixtures of dyfistuffs of Claim 1 of the 9. Dyestuffor mixtures of dyestuffs of claim 1 of the formula formula R t l R 011m 4 x O I! CH N-N (R wherein 6 n R,. R R R m. and X are defined as in claim 1;

R :is hydrogen, C,-C -alkyl, benzyl or phenylethyl;

R is halo. nitro, C -C ulkyl, benzyl, phenylethyl, hy-

droxy C -C alkoxy. phenyloxy, or benzyloxy; and

W is the number 0, l or 2.

l. Dyestuff or mixtures of dyestuffs of claim 1 of the formula wherein and v R, R R R R R X, m and n are defined as in 011 claim 6. l0. Mixture of the dyestuffs of the formulae 01..

0 l" ClI QI-N c1 13. Mixture of the dyestuffs of the formulae and 3 I CH=CH-N -K O! 3 I 3 o .11 0 1 C11 and P 11. Mixture of the dyestuffs of the formulae CI=CI N H4! 01' C1 R (k 14 0! 14. Mixture of the dyestuffs of the formulae 3 c1 and H (Jilli 40 I cn=cn-u c1 c1 01'' Cl 11/ 3 3 e11 Cl=CI-H C13 and 3 (:11

I2. Mixture of the dyestuffs of the formulae 

1. DYESTUFF OF THE FORMULA OR MIXTURES OF DYESTUFFS OF THE FORMULA
 2. Dyestuff or mixtures of dyestuffs of claim 1 of the formula
 3. Dyestuff or mixtures of dyestuffs of claim 1 of the formula
 4. Dyestuff or mixtures of dyestuffs of claim 1 of the formula
 5. Dyestuff or mixtures of dyestuffs of claim 1 of the formula
 6. Dyestuff or mixtures of dyestuffs of claim 1 of the formula
 7. Dyestuff or mixtures of dyestuffs of claim 1 of the formula
 8. Dyestuff or mixtures of dyestuffs of claim 1 of the formula
 9. Dyestuff or mixtures of dyestuffs of claim 1 of the formula
 10. Mixture of the dyestuffs of the formulae
 11. Mixture of the dyestuffs of the formulae
 12. Mixture of the dyestuffs of the formulae
 13. Mixture of the dyestuffs of the formulae
 14. Mixture of the dyestuffs of the formulae 